Designing Electrophilic and Nucleophilic Dual Centers in the ReS₂ Plane toward Efficient Bifunctional Catalysts for Li-CO₂ Batteries

Abstract

Two-dimensional transition metal dichalcogenides (TMDCs) show great potential as efficient catalysts for Li-CO 2 batteries. However, the basal plane engineering on TMDCs toward bifunctional catalysts for Li-CO 2 batteries is still poorly understood. In this work, density functional theory calculations reveal that nucleophilic N dopants and electrophilic S vacancies in the ReS 2 plane tailor the interactions with Li atoms and C/O atoms in intermediates, respectively. The electrophilic and nucleophilic dual centers show suitable adsorption with all intermediates during discharge and charge, resulting in a small energy barrier for the rate-determining step. Thus, an efficient bifunctional catalyst is produced toward Li-CO 2 batteries. As a result, the optimal catalyst achieves an ultrasmall voltage gap of 0.66 V and an ultrahigh energy efficiency of 81.1% at 20 μA cm −2 , which is superior to those of previous catalysts under similar conditions. The introduction of electrophilic and nucleophilic dual centers provides new avenues for designing excellent bifunctional catalysts for Li-CO 2 batteries.

Atomically miniaturized bi-phase IrOx/Ir catalysts loaded on N-doped carbon nanotubes for high-performance Li–CO2 batteries

“…To calculate the rates of the CO 2 reduction and evolution reactions (CRR and CER, or discharging and charging, respectively) occurring in a Li–CO 2 battery, the following reaction steps and adsorbates were considered. 46–49 …”

Carbon Tube-Based Cathode for Li-CO2 Batteries: A Review

“…In previous work, ruthenium-based materials were considered efficient catalysts for lithium carbonate decomposition [33,34]. Chen et al anchored Ru nanoparticles on carbon tubes, which could effectively improve the conductivity of the material matrix, and the porous skeleton formed by cross-linking could promote the diffusion and transmission of CO 2 and the electrolyte [35].…”

“…Transition metal dichalcogenides have been widely investigated in various electrochemical reactions, including Li-CO 2 batteries [34,49]. The composites of MoS 2 and CNTs also realized a stable cycle in Li-CO 2 batteries [50].…”

All-Solid-State Photo-Assisted Li-CO2 Battery Working at an Ultra-Wide Operation Temperature

“…In the recent past, aprotic Li-CO 2 batteries, which have caught the eyes of researchers as a consequence of their dual functions of CO 2 utilization and energy storage, have shown a high theoretical energy density (1876 Wh kg –1 ) . As is well-known, fast kinetics for CO 2 reduction and evolution reactions (CDRR/CDER) at the cathodes is necessary for the Li-CO 2 batteries . Therefore, various efforts have been directed to developing various efficient catalysts ( e.g ., carbon materials, , metal-based materials, , metal/covalent-organic frameworks, , and redox mediators) .…”